• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Die Herstellung von Aldehyden durch Umsetzung von Olefinen mit Kohlenmonoxid und Wasserstoff erfolgt in Gegenwart von Rhodium in metallischer Form oder als Verbindung und einem wasserlöslichen quartären Ammoniumsalz eines mono-, di- oder trisulfonierten Arylphosphins als Katalysator.
    公开号:SU1537134A3
    申请号:SU853884106
    申请日:1985-04-26
    公开日:1990-01-15
    发明作者:Барманн Гельмут；Корнильс Бой；Конколь Вернер；Липпс Вольфганг
    申请人:Рурхеми Аг (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to methods for producing aldehydes C7 or C) 5 used in organic synthesis.
    The purpose of the invention is to reduce the loss of parents and the philosopher.
    Example 1. In a 1 liter autoclave with a immersion fitting, 315 g (corresponding to 295 ml) of an aqueous solution of three (m-sulfophenyl) phosphine trimethylbenzylammonium salt with a P (III) content of 0.308 wt.% And 400 rpm of rhodium are fed. as an acetate. Then, synthesis gas (CO / H4 T: 1) is fed to a pressure of 25 atm. The reaction solution is treated with synthesis gas for 3 hours while stirring at 125 ° C. Then it is cooled to approximately 30 ° C, the stirring is stopped, and after suction for 15 minutes, the excess pressure solution is withdrawn through the immersion fitting ("61 g) for analysis. The residual solution remains in the autoclave. While stirring with the pump, 158 g of n-hexene-1 was added to it. Maintaining the pressure at a level of 25 atm, the mixture is heated to 125 ° C for 3 hours. Then it is cooled to 30 ° C and after suction for 15 minutes the excess organic phase is discharged through the immersion nozzle. The resulting organic phase is weighed and subjected to chromatographic analysis.
    The hydroformylation process is repeated eight times.
    cl
    00
    h |
    them
    00
    J
    s
    Table 1 shows the activity indicators of the aqueous and organic phases. To determine the amount of rhodium and phosphorus carried out with the organic phase, the organic components removed in each experiment are combined, concentrated to about 1/10 of the initial amount and analyzed. In this case, 0.013 ppm of rhodium and 0.38 ppm of phosphorus are obtained (based on the initial amount of the organic phase),
    Examples 2-5. The process is carried out analogously to example 1, but using 420 g (390 ml) of an aqueous solution containing 46 May L of the dodecyl ethyl methylammonium salt of tri- (m-sulfophenyl) phosphine (Example 2); 420 g (375 ml) of an aqueous solution containing 1 st 22 wt.% Sodium salt of tri- (m-sulfophenyl) phosphine and 21 g (5% by weight of the solution) of trimethyl hexadecyl ammonium bromide (Example 3 prototype); 820 g (740 ml) of an aqueous solution containing 27% by weight of benzyltrimethylammonium salt of di- (m-sulfophenyl) phosphine (Example 4); 420 g (390 ml) of an aqueous solution containing 23% by weight of benzyltriethylammonium salt of tri- (m-sulfo-phenyl) phosphine (Example 5)
    The results of the experiments, which are the average values of the indicated number of hydroformylation processes, are summarized in Table 2.
    Examples 6-9. The process is carried out analogously to example 1, but styrene and n-octene are used as an olefin. In this case, by examples 5 and 6 (according to the prototype) an aqueous solution of tri (m-sulfophenyl) phosphine sodium salt (420 g, corresponding to 375 ml of 22% solution and 9.75 g of tetradecyltrimethylammonium metasulfate, and in examples 7 and 8 - the dodecyl ethyl dimethylammonium salt (420 g, which corresponds to 391 ml of 23%



    ten
    15
    20
    25
    thirty
    35
    - ABOUT
    45
    344
    solution) tri- (m-sulfophenyl) phosphine.
    The results of the experiments are summarized in table 3.
    Examples 10 and 11. The process is carried out analogously to example 1 with the difference that tetradecene-1 is used as an olefin.
    In addition, according to Example 10 (according to the prototype), an aqueous solution of sodium tri- (m-sulfophenyl) -phosphine (420 g, which corresponds to 375 ml of 22% rasgesra) and 9.75 g of tetradecyltrimethylammonium metasulfate are used, and Example 11 — an aqueous solution of a tetradecyltrimethylammonium salt (420 g, which corresponds to 395 ml of a 20% solution) of tri- (m-sulfophenyl) phosphine,
    The results of the experiments are summarized in table 4.
    The proposed method allows reducing the loss of rhodium and phosphorus to 0.019-0.025 and 0.38-0.4% respectively against 0.3-0.45 and 4-6% in the known method.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing aldehydes C-, Cd or C (j by reacting a corresponding olefin with carbon monoxide and hydrogen in the liquid phase at 125 ° C and 25 atm on a rhodium catalyst in the presence of water and a water soluble salt of sulfonated phenylphosphine and the subsequent isolation of the target product, characterized in that In order to reduce the loss of rhodium and phosphorus, dodecyl dimethylammonium, tetradecyltrimethyl ammonium, benzyltrimethylammonium, benzyltrimethylammonium sulphate are used as the water soluble sulfonated phenylphosphine sulfide. and the trimethylbenzylammonium salt of di- or tri- (m-sulfophenyl) phosphine,
    Table 1
    Conversion (according to gas chromatography),% 48 Ratio of n / and aldehyde C7 93/7 Aqueous phase in a reactor, g 315
    r-atom rhodi min Number of hydroformylation with the same catalyst solution
    Losses give birth, rsh Losses in phosphorus, rsh
    153713 16
    . Continuation of the table. one
    Table 3
    five
    , b
    5 0.3
    five
    5 0.02
    0,
    five
    0.02 O, A.
    1537131 8
    Table t
    Olefin-Tetradecene-1 Tetradec
    Conversion (according to
    gas chromatography),% 18,692
    The ratio of n / i-aldehyde 8V1682 / 18
    Activity, albaegida..k6
    r-atom rodi min
    The number of hydroformylation with the same solution of catalyst55 Loss of rhodium, prsh Q 0.025 Loss of phosphorus, ppm c 0.4
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1537134A3|1990-01-15|Method of producing aldehydes c7, c9 or c15
    US4248802A|1981-02-03|Catalytic hydroformylation of olefins
    EP0375573B1|1993-03-17|Low pressure rhodium catalyzed hydroformylation of olefins
    EP0073961B1|1985-08-21|Hydroformylation process using a rhodium complex catalyst with biphosphine monoxide ligands
    Barton et al.1991|Aqueous soluble organometallic complexes
    CA1183123A|1985-02-26|Hydroformylation process using triarylphosphine andbisphosphine monooxide ligands
    US4297239A|1981-10-27|Hydroformylation catalyst reactivation
    EP0024088A1|1981-02-25|Process for the preparation of aldehydes
    US4593126A|1986-06-03|Process for preparing aldehydes
    EP0019296A1|1980-11-26|Process for removing triorganophosphine from a liquid composition
    US4578523A|1986-03-25|Process for the preparation of aldehydes
    FR2511613A1|1983-02-25|ORGANOMETALLIC COMPLEXES AND THEIR USE AS HOMOGENEOUS CATALYSTS
    US4889957A|1989-12-26|Dinuclear and water-soluble rhodium complexes and hydroformylation catalysis therewith
    CA1081257A|1980-07-08|Control of condensation products in hydroformylation process
    US4108905A|1978-08-22|Catalytic reactions
    EP0102341B1|1986-11-20|Improved hydroformylation process to prepare glycol aldehydes
    US4879418A|1989-11-07|Process for the preparation of aldehydes
    AU593958B2|1990-02-22|Process for the preparation of aldehydes
    EP0017183B1|1984-04-25|Hydroformylation medium, process of production thereof and process for producing aldehydes using the hydroformylation medium
    US4593011A|1986-06-03|Hydroformylation process using triarylphosphine and bisphosphine monooxide ligands
    CA1106857A|1981-08-11|Process for the preparation of 3-| butyraldehyde
    JPH0755834B2|1995-06-14|Method for recovering rhodium from distillation residue of oxo synthesis product
    EP0186075B1|1990-02-28|Process for the preparation of 8- and 9-formyl-tricyclo-|-decene-3
    US4680168A|1987-07-14|Extraction of Group 8 metals from organic solutions
    AU593699B2|1990-02-15|A process for the preparation of aldehydes
    同族专利:
    公开号 | 公开日
    EP0163234B1|1990-02-28|
    DE3420491A1|1985-12-05|
    DE3576150D1|1990-04-05|
    KR880001353B1|1988-07-28|
    ZA853971B|1986-01-29|
    HUT39703A|1986-10-29|
    EP0163234A3|1987-05-27|
    JPH0140019B2|1989-08-24|
    RO91880A|1987-07-30|
    JPS611633A|1986-01-07|
    PL253588A1|1986-02-11|
    CA1244053A|1988-11-01|
    AU4321885A|1985-12-05|
    AT50556T|1990-03-15|
    RO91880B|1987-07-31|
    AU577382B2|1988-09-22|
    HU204249B|1991-12-30|
    KR860000237A|1986-01-27|
    BR8502451A|1986-01-28|
    EP0163234A2|1985-12-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3928232A|1972-10-24|1975-12-23|Chevron Res|Aryl sulfonate stabilized cobalt carbonyl complex compounds|
    FR2314910B1|1975-06-20|1977-12-02|Rhone Poulenc Ind|
    US4248802A|1975-06-20|1981-02-03|Rhone-Poulenc Industries|Catalytic hydroformylation of olefins|
    NO156742C|1979-03-28|1987-11-18|Union Carbide Corp|PROCEDURE FOR THE PREPARATION OF A HYDROFORMAL MEDIUM AND THE PROCESS FOR THE PREPARATION OF ALDEHYDES.|
    FR2473504B1|1979-10-31|1984-01-20|Rhone Poulenc Chim Base|
    GB2085874B|1980-09-04|1984-08-08|Johnson Matthey Plc|Hydroformylation of olefins|
    DE3234701A1|1982-09-18|1984-04-05|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR PRODUCING ALDEHYDES|
    DE3413427A1|1984-04-10|1985-10-17|Ruhrchemie Ag, 4200 Oberhausen|METHOD FOR PRODUCING ALDEHYDES|DE3420493A1|1984-06-01|1985-12-05|Ruhrchemie Ag, 4200 Oberhausen|QUARTERS OF AMMONIUM SALTS OF SULPHONED TRIARYLPHOSPHINS|
    DE3534314A1|1985-09-26|1987-04-02|Ruhrchemie Ag|METHOD FOR PRODUCING ALDEHYDES|
    DE3546123A1|1985-12-24|1987-06-25|Ruhrchemie Ag|METHOD FOR PRODUCING ALDEHYDES|
    DE3616057A1|1986-05-13|1987-11-19|Ruhrchemie Ag|METHOD FOR PRODUCING ALDEHYDES|
    US4716250A|1986-07-10|1987-12-29|Union Carbide Corporation|Hydroformylation using low volatile/organic soluble phosphine ligands|
    US4825003A|1986-09-17|1989-04-25|Mitsui Toatsu Chemicals, Incorporated|Production process of 2-chloropropionaldehyde|
    US4731486A|1986-11-18|1988-03-15|Union Carbide Corporation|Hydroformylation using low volatile phosphine ligands|
    US5113022A|1988-08-05|1992-05-12|Union Carbide Chemicals & Plastics Technology Corporation|Ionic phosphites used in homogeneous transition metal catalyzed processes|
    DE3942954A1|1989-12-23|1991-06-27|Hoechst Ag|PROCESS FOR THE PREPARATION OF ALDEHYDE|
    FR2671078A1|1990-12-31|1992-07-03|Rhone Poulenc Chimie|REAGENT AND METHOD FOR THREE - PHASE HYDROCARBONYLATION.|
    US5288818A|1991-08-20|1994-02-22|Exxon Chemical Patents Inc.|Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|
    US5215667A|1991-08-20|1993-06-01|Exxon Chemical Patents Inc.|Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction|
    DE4242725A1|1992-12-17|1994-06-23|Hoechst Ag|Process for the production of higher, predominantly unbranched, primary alcohols|
    DE4440552A1|1994-11-12|1996-05-15|Hoechst Ag|Process for the preparation of formyl carboxylic acid esters|
    US6756411B2|1995-06-29|2004-06-29|Sasol TechnologyLimited|Process for producing oxygenated products|
    KR100451631B1|2002-05-17|2004-10-08|주식회사 바름인|Preparation of fermented soybean product enriched γ-aminobutylic acid and phytoestrogens using Bifidobacterium breve K-110 of korean-type lactic acid bacteria|
    KR100460697B1|2002-06-01|2004-12-09|고을빛 생식마을 |Manufacturing Method for Soaking and Germinated Soybean Containing High Isoflavone|
    DE102008044783B4|2008-08-28|2012-05-16|Oxea Gmbh|Process for the recovery of aliphatic C3 to C10 aldehydes from high boilers by thermal treatment|
    DE102009004655B4|2009-01-15|2013-02-14|Oxea Gmbh|Process for the preparation of aldehydes|
    DE102009016651B4|2009-04-07|2011-11-17|Oxea Gmbh|Process for the preparation of aldehydes|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19843420491|DE3420491A1|1984-06-01|1984-06-01|METHOD FOR PRODUCING ALDEHYDES|
    [返回顶部]